Dip, spray, and flow coating process for forming coated articles

ABSTRACT

This invention relates to methods and apparatus for making coated articles with one or more layers by dip, spray or flow coating. In one aspect, this invention relates to an apparatus and method for making coated containers, preferably comprising polyethylene terephthalate, from coated preforms. In preferred embodiments, the apparatus and method permit the coated container or preform to be made in an energy-efficient manner that reduces the danger of coating damage and thus increases the efficacy of the final container.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.10/614,731 filed Jul. 3, 2003, currently pending, which is acontinuation of PCT/US03/22333, filed Jul. 3, 2003, and which claimspriority to provisional applications Ser. No. 60/394,092 filed Jul. 3,2002, Ser. No. 60/422,251 filed Oct. 28, 2002, and Ser. No. 60/441718filed Jan. 23, 2003. All of these prior applications are herebyexpressly incorporated by reference in their entireties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to methods and apparatus for making coatedarticles with one or more layers by dip, spray or flow coating. In oneaspect, this invention relates to an apparatus and method for makingcoated containers, preferably comprising polyethylene terephthalate,from coated preforms.

2. Description of the Related Art

Preforms are the products from which containers are made by blowmolding. Unless otherwise indicated the term “container” is a broad termand is used in its ordinary sense and includes, without limitation, boththe preform and bottle container therefrom. A number of plastic andother materials have been used for containers and many are quitesuitable. Some products such as carbonated beverages and foodstuffs needa container, which is resistant to the transfer of gases such as carbondioxide and oxygen. Coating of such containers has been suggested formany years. A resin now widely used in the container industry ispolyethylene terephthalate (PET), by which term we include not only thehomopolymer formed by the polycondensation of [beta]-hydroxyethylterephthalate but also copolyesters containing minor amounts of unitsderived from other glycols or diacids, for example isophthalatecopolymers.

The manufacture of biaxially oriented PET containers is well known inthe art. Biaxially oriented PET containers are strong and have goodresistance to creep. Containers of relatively thin wall and light weightcan be produced that are capable of withstanding, without unduedistortion over the desired shelf life, the pressures exerted bycarbonated liquids, particularly beverages such as soft drinks,including colas, and beer.

Thin-walled PET containers are permeable to some extent to gases such ascarbon dioxide and oxygen and hence permit loss of pressurizing carbondioxide and ingress of oxygen which may affect the flavor and quality ofthe bottle contents. In one method of commercial operation, preforms aremade by injection molding and then blown into bottles. In the commercialtwo-liter size, a shelf life of 12 to 16 weeks can be expected but forsmaller bottles, such as half liter, the larger surface-to-volume ratioseverely restricts shelf life. Carbonated beverages can be pressured to4.5 volumes of gas but if this pressure falls below acceptable productspecific levels, the product is considered unsatisfactory.

It is therefore desirable to provide the container with a layer of abarrier material which has a low vapor and gas permeability. Barrierlayers may be provided by a variety of techniques, includingcoinjection, chemical vapor deposition, plasma coating with amorphouscarbon and/or SiOx, etc., so as to form a laminar coated container.Other examples involve the use of an aqueous dispersion of barrierpolymers, and have included dispersions made from vinylidene chloridewith acrylonitrile and/or methyl acrylate, optionally containing unitsderived from other monomers such as methyl methacrylate, vinyl chloride,acrylic acid, or itaconic acid, dispersions made from EVOH and MXD6,etc. The dispersions typically contained surfactants such as sodiumalkyl sulphonates.

SUMMARY OF THE INVENTION

In one aspect, this invention relates to methods and apparatus formaking articles, preferably plastic articles, having coatings comprisingone or more layers. These layers may comprise thermoplastic materialswith good gas-barrier characteristics as well as layers that provide UVprotection, scuff resistance, blush resistance, chemical resistance,and/or active properties such as O₂ or CO₂ scavenging.

In a preferred embodiment, there is provided a process for theproduction of a coated article. The process comprises providing anarticle, preferably a container or preform comprising polyethyleneterephthalate; applying to said article a coating of an aqueousdispersion of a thermoplastic epoxy resin to the article; andcuring/drying the coating. In embodiments where the article is apreform, the method preferably further comprises a blow moldingoperation, preferably including stretching the dried coated preformaxially and radially, in a blow molding process, at a temperaturesuitable for orientation, into a bottle-container. In the process thethermoplastic epoxy coating is applied by dip, spray, or flow coating ofthe article and the coating and drying is applied in more than one passsuch that the coating properties are increased with each coating layer.The volume of coating deposition may be altered by the articletemperature, the article angle, the solution/dispersion temperature, thesolution/dispersion viscosity and the number of layers. The multiplecoatings of preferred processes result in multiple layers withsubstantially no distinction between layers, improved coatingperformance and/or reduction of surface voids and coating holidays. Inaddition, a preferred multiple coating process results in successivelayers requiring decreasing amounts of coating material to thoroughlycoat the article.

In preferred embodiments, the coating and drying process results inenhanced surface tension properties. Furthermore, in preferredprocesses, the drying process of articles has a repairing effect onsurface defects of the finished article. In addition, in preferredprocesses, the drying/curing process produces articles which exhibitsubstantially no blushing.

In accordance with one embodiment, there is provided a process formaking thermoplastic resin coated articles, the process comprising:applying an aqueous solution or dispersion of a first thermoplasticresin on the outer surface of an article substrate by dip, spray, orflow coating; withdrawing the article from the dip, spray, or flowcoating at a rate so as to form a first coherent film; curing/drying thecoated article until the first film is substantially dried so as to forma first coating. Optionally, the method may further include applying anaqueous solution or dispersion of a second thermoplastic resin on theouter surface of an article substrate by dip, spray, or flow coating;withdrawing the article from the dip, spray, or flow coating at a rateso as to form a second coherent film; curing/drying the coated articleuntil the second film is substantially dried so as to form a secondcoating. In preferred embodiments, at least one of the first and secondthermoplastic resins comprises a thermoplastic epoxy resin, and thefirst and second resins may be the same or different.

In accordance with a preferred embodiment, a method for dip coatingarticles is provided comprising the steps of: a) dipping the articleinto an aqueous coating solution/dispersion contained either in a staticvat or in a flow coater with the article rotating to achieve fullexposure to the flow; b) withdrawing the article from the static vat orflow coater below the rate at which a coherent film is observed; and c)exposing the article and film to infrared heaters until the film issubstantially dried, optionally while cooling the article with air.

In accordance with a preferred embodiment, an apparatus for dip coatingarticles is provided comprising: an article conveyor that transports thearticles through a dip coating system; a tank or vat containing anaqueous solution/dispersion coating material wherein the conveyor drawsor dips the articles through the tank or vat; and a curing/drying unitwhich comprises an oven or chamber in which a curing/drying source islocated, wherein the articles are moved through the oven or chamber bythe conveyor. The curing/drying unit is optionally coupled with a fan orblower for cooling the article with air. A preferred apparatus mayfurther comprise a second tank or vat of coating material and a secondcuring/drying unit. In another preferred apparatus, the conveyortransports the articles back through the tank and/or the curing/dryingunit to provide a second coating on the article. A preferred apparatusmay optionally include one or more drip removers positioned between thecoating tank or vat and the curing/drying unit, or elsewhere before thecuring/drying unit.

In accordance with another preferred embodiment, a method for coatingarticles is provided comprising the steps of: a) spray coating thearticle with an aqueous coating solution/dispersion with the articlerotating to achieve full exposure to the flow, b) spraying the articleat a rate which a coherent film is observed; and c) exposing the articleand film to infrared heaters until the film is substantially dried;optionally while cooling the article with air.

In accordance with a preferred embodiment, an apparatus for spraycoating articles is provided comprising: an article conveyor thattransports the articles through a spray coating system; one or morespray nozzles is in fluid communication with an aqueoussolution/dispersion of coating material, such as may be contained in atank or vat; a coating material collector which receives unused coatingmaterial; and a curing/drying unit which comprises an oven or chamber inwhich a curing/drying source is located, wherein the articles are movedthrough the oven or chamber by the conveyor. The curing/drying unit isoptionally coupled with a fan or blower for cooling the article withair. A preferred apparatus may further comprise a second tank or vat ofcoating material, a second grouping of one or more spray nozzles, and/ora second curing/drying unit, or, in providing a second coating, one ormore components of the first spray coating system may be used. Apreferred apparatus may optionally include one or more drip removerspositioned between the sprayer and the curing/drying unit, or elsewherebefore the curing/drying unit.

In accordance with another preferred embodiment, a method for flowcoating articles is provided comprising the steps of: a) flow coatingthe article with an aqueous coating solution/dispersion with the articlerotating to achieve full exposure to the flow, b) withdrawing thearticle from sheet of the flow coating at a rate which a coherent filmis observed; c) exposing the article and film to infrared heaters untilthe film is substantially dried; and optionally d) cooling the articlewith air.

In accordance with a preferred embodiment, an apparatus for flow coatingarticles is provided comprising: an article conveyor that transports thearticles through a flow coating system; a tank or vat containing anaqueous solution/dispersion of coating material that is in fluidcommunication with a fluid guide, wherein the coating material flows offof the fluid guide forming a sheet or falling shower curtain; a coatingmaterial collector which receives unused coating material; and acuring/drying unit which comprises an oven or chamber in which acuring/drying source is located, wherein the articles are moved throughthe oven or chamber by the conveyor. The curing/drying unit isoptionally coupled with a fan or blower for cooling the article withair. A preferred apparatus may further comprise a second tank or vat ofcoating material, a second fluid guide, and/or a second curing/dryingunit, or, in providing a second coating, one or more components of thefirst flow coating system may be used. A preferred apparatus mayoptionally include one or more drip removers positioned between thecoating tank or vat and the curing/drying unit, or elsewhere before thecuring/drying unit.

In one embodiment, a preferred apparatus includes means for entry of thearticle into the system; dip, spray, or flow coating of the article;optionally removal of excess material; drying or curing; optionally,cooling, during and/or after drying/curing, and ejection from thesystem. In one embodiment the apparatus is a single integratedprocessing line that contains multiple stations wherein each stationcoats the article thereby producing a article with multiple coatings. Inanother embodiment, the system is modular wherein each processing lineis self-contained with the ability to handoff to another line, therebyallowing for single or multiple coatings depending on how many modulesare connected thereby allowing maximum processing flexibility.

In accordance with one embodiment, there is provided a multilayerarticle comprising: a substrate, and at least one layer comprisingthermoplastic epoxy resin coating material disposed on at least aportion of said substrate to form a coated article, wherein the coatedarticle preferably exhibits substantially no blushing or whitening whenimmersed in water or otherwise directly exposed to water. In preferredembodiments, such articles also exhibit substantially no blushing orwhitening when exposed to high humidity, including humidity of about 70%or higher. Such exposure or immersion to water or high humidity mayoccur for several hours or longer, including about 6 hours, 12 hours, 24hours, 48 hours, and longer and/or may occur at temperatures around roomtemperature and at reduced temperatures. In one embodiment, the coatedarticles exhibit substantially no blushing or whitening when immersed inor otherwise exposed directly to water at a temperature of about 0° C.to 30° C., including about 5° C., 10° C., 15° C., 20° C., 22° C., and25° C. for about 24 hours. In preferred embodiments, the substratecomprises a polymeric material, preferably a thermoplastic materialchosen from the group consisting of polyester, polypropylene,polyethylene, polycarbonate, polyamides and acrylics. In embodimentswherein the article is a preform or bottle having a body portion andneck portion, the coating is preferably disposed substantially only onthe body portion of the preform. In a preferred embodiment, one or moreadditional coating layers are disposed on the article. In such three ormore layer embodiments, preferably there is substantially no distinctionbetween coating layers, and/or one or more additional layers comprisethermoplastic materials. The coating layer(s) may contain one or more ofthe following characteristics in preferred embodiments: gas-barrierprotection, UV protection, scuff resistance, blush resistance, chemicalresistance.

In accordance with a preferred embodiment a multilayer container isproduced, preferably a preform or bottle having a body portion and neckportion. Preferably the container, preform or bottle comprises athermoplastic material substrate and one or more, layers ofthermoplastic resin coating material. Preferably the thermoplasticsubstrate material is chosen from the chosen from the group consistingof polyesters, polyolefins, polycarbonates, polyamides and acrylics.Preferably the coating layers contain one or more of the followingcharacteristics: gas-barrier protection, UV protection, scuffresistance, blush resistance, chemical resistance. Preferably thecoating is disposed substantially only on the body portion of thepreform. In addition, the finished product preferably has substantiallyno distinction between layers.

In a preferred embodiment, the coated article or container formed from acoated preform shows substantially no blushing or whitening when exposedto water or high humidity at room temperature or reduced or elevatedtemperatures (with respect to room temperature) for a period of severalhours or longer. In one embodiment, the coated article or containerexhibits substantially no blushing when immersed in or otherwise exposedto water. In related embodiments, the infrared heating is replaced withflame curing, gas heaters, electron beam processing, or UV radiationoptionally followed by or combined with cooling with air.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments of the presentinventions will become readily apparent to those skilled in the art fromthe following detailed description of a preferred embodiments havingreference to the attached figures, the invention not being limited toany particular preferred embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an uncoated preform as is used as a starting material forpreferred embodiments.

FIG. 2 is a cross-section of a preferred uncoated preform of the typethat is coated in accordance with a preferred embodiment.

FIG. 3 is a cross-section of one preferred embodiment of a coatedpreform.

FIG. 4 is an enlargement of a section of the wall portion of a coatedpreform.

FIG. 5 is a cross-section of another embodiment of a coated preform.

FIG. 6 is a cross-section of a preferred preform in the cavity of ablow-molding apparatus of a type that may be used to make a preferredcoated container of an embodiment of the present invention.

FIG. 7 is a coated container prepared in accordance with a blow moldingprocess.

FIG. 8 is a cross-section of one preferred embodiment of a coatedcontainer having features in accordance with the present invention.

FIG. 9 is a three-layer embodiment of a preform.

FIG. 10 there is a non-limiting flow diagram that illustrates apreferred process.

FIG. 11 is a non-limiting flow diagram of one embodiment of a preferredprocess wherein the system comprises a single coating unit.

FIG. 12 is a non-limiting flow diagram of a preferred process whereinthe system comprises multiple coating units in one integrated system.

FIG. 13 is a non-limiting flow diagram of a preferred process whereinthe system comprises multiple coating units in a modular system.

FIG. 14 is a non-limiting top view of one embodiment of a preferredprocess wherein the system comprises a single flow coating unit.

FIG. 15 is a non-limiting front view of one embodiment of a preferredprocess wherein the system comprises a single flow coating unit.

FIG. 16 is a non-limiting cross section view of one embodiment of apreferred process wherein the system comprises a single flow coatingunit.

FIGS. 17A and 17B depict non-limiting views of one embodiment of apreferred IR drying/curing unit.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Methods and apparatus for coating articles comprising one or more layersare described herein. These layers may comprise thermoplastic materialswith good gas-barrier characteristics as well as layers or additivesthat provide UV protection, scuff resistance, blush resistance, chemicalresistance, and/or active properties for O₂ and/or CO₂ scavenging.

As presently contemplated, one embodiment of a coated article is apreform of the type used for beverage containers. Alternatively,embodiments of the coated articles of the present invention could takethe form of jars, tubes, trays, bottles for holding liquid foods,medical products, or other products sensitive to gas exposure. However,for the sake of simplicity, these embodiments will be described hereinprimarily as articles or preforms.

Furthermore, the articles described herein may be described specificallyin relation to a particular substrate, polyethylene terephthalate (PET),but preferred methods are applicable to many other thermoplastics of thepolyester type. As used herein, the term “substrate” is a broad termused in its ordinary sense and includes embodiments wherein “substrate”refers to the material used to form the base article that is coated.Other suitable article substrates include, but are not limited to,various polymers such as polyesters, polyolefins, includingpolypropylene and polyethylene, polycarbonate, polyamides, includingnylons, or acrylics. These substrate materials may be used alone or inconjunction with each other. More specific substrate examples include,but are not limited to, polyethylene 2,6- and 1,5-naphthalate (PEN),PETG, polytetramethylene 1,2-dioxybenzoate and copolymers of ethyleneterephthalate and ethylene isophthalate.

In one embodiment, PET is used as the polyester substrate which iscoated. As used herein, “PET” includes, but is not limited to, modifiedPET as well as PET blended with other materials. One example of amodified PET is “high IPA PET” or IPA-modified PET. The term “high IPAPET” refers to PET in which the IPA content is preferably more thanabout 2% by weight, including about 2-10% IPA by weight.

One or more layers of a coating material are employed in preferredmethods and processes. The layers may comprise barrier layers, UVprotection layers, oxygen scavenging layers, carbon dioxide scavenginglayers, and other layers as needed for the particular application. Asused herein, the terms “barrier material,” “barrier resin,” and the likeare broad terms and are used in their ordinary sense and refer, withoutlimitation, to materials which, when used to coat articles, preferablyadhere well to the article substrate and have a lower permeability tooxygen and carbon dioxide than the article substrate. As used herein,the terms “UV protection” and the like are broad terms and are used intheir ordinary sense and refer, without limitation, to materials which,when used to coat articles, preferably adhere well to the articlesubstrate and have a higher UV absorption rate than the articlesubstrate. As used herein, the terms “oxygen scavenging” and the likeare broad terms and are used in their ordinary sense and refer, withoutlimitation, to materials which, when used to coat articles, preferablyadhere well to the article substrate and have a higher oxygen absorptionrate than the article substrate. As used herein, the terms “carbondioxide scavenging” and the like are broad terms and are used in theirordinary sense and refer, without limitation, to materials which, whenused to coat articles, preferably adhere well to the article substrateand have a higher carbon dioxide absorption rate than the articlesubstrate. As used herein, the terms “crosslink,” “crosslinked,” and thelike are broad terms and are used in their ordinary sense and refer,without limitation, to materials and coatings which vary in degree froma very small degree of crosslinking up to and including fully crosslinked materials such as a thermoset epoxy. The degree of crosslinkingcan be adjusted to provide the appropriate degree of chemical ormechanical abuse resistance for the particular circumstances.

Once a suitable coating material is chosen, an apparatus and method forcommercially manufacturing a coated article is necessary. One suchmethod and apparatus is described below.

Preferred methods provide for a coating to be placed on an article,specifically a preform, which is later blown into a bottle. Such methodsare, in many instances, preferable to placing coatings on the bottlesthemselves. Preforms are smaller in size and of a more regular shapethan the containers blown therefrom, making it simpler to obtain an evenand regular coating. Furthermore, bottles and containers of varyingshapes and sizes can be made from preforms of similar size and shape.Thus, the same equipment and processing can be used to coat preforms toform several different types of containers. The blow-molding may takeplace soon after molding and coating, or preforms may be made and storedfor later blow-molding. If the preforms are stored prior toblow-molding, their smaller size allows them to take up less space instorage. Even though it is often times preferable to form containersfrom coated preforms, containers may also be coated.

The blow-molding process presents several challenges. One step where thegreatest difficulties arise is during the blow-molding process where thecontainer is formed from the preform. During this process, defects suchas delamination of the layers, cracking or crazing of the coating,uneven coating thickness, and discontinuous coating or voids can result.These difficulties can be overcome by using suitable coating materialsand coating the preforms in a manner that allows for good adhesionbetween the layers.

Thus, preferred embodiments comprise suitable coating materials. When asuitable coating material is used, the coating sticks directly to thepreform without any significant delamination and will continue to stickas the preform is blow-molded into a bottles and afterwards. Use of asuitable coating material also helps to decrease the incidence ofcosmetic and structural defects which can result from blow-moldingcontainers as described above.

One common problem seen in articles formed by coating using coatingsolutions or dispersions is “blushing” or whitening when the article isimmersed in (which includes partial immersion) or exposed directly towater or high humidity (which includes at or above about 70% relativehumidity). In preferred embodiments, the articles disclosed herein andthe articles produced by methods disclosed herein exhibit minimal orsubstantially no blushing or whitening when immersed in or otherwiseexposed directly to water or high humidity. Such exposure may occur forseveral hours or longer, including about 6 hours, 12 hours, 24 hours, 48hours, and longer and/or may occur at temperatures around roomtemperature and at reduced temperatures, such as would be seen byplacing the article in a cooler containing ice or ice water. Exposuremay also occur at an elevated temperature, such elevated temperaturegenerally not including temperatures high enough to cause an appreciablesoftening of the materials which form the container or coating,including temperatures approaching the Tg of the materials. In oneembodiment, the coated articles exhibit substantially no blushing orwhitening when immersed in or otherwise exposed directly to water at atemperature of about 0° C. to 30° C., including about 5° C., 10° C., 15°C., 20° C., 22° C., and 25° C. for about 24 hours. The process used forcuring or drying coating layers appears to have an effect on the blushresistance of articles.

B. Detailed Description of the Drawings

Referring to FIG. 1, a preferred uncoated preform 1 is depicted. Thepreform is preferably made of an FDA approved material such as virginPET and can be of any of a wide variety of shapes and sizes. The preformshown in FIG. 1 is a 24 gram preform of the type which will form a 16oz. carbonated beverage bottle, but as will be understood by thoseskilled in the art, other preform configurations can be used dependingupon the desired configuration, characteristics and use of the finalarticle. The uncoated preform 1 may be made by injection molding as isknown in the art or by other suitable methods.

Referring to FIG. 2, a cross-section of a preferred uncoated preform 1of FIG. 1 is depicted. The uncoated preform 1 has a neck portion 2 and abody portion 4. The neck portion 2, also called the neck finish, beginsat the opening 18 to the interior of the preform 1 and extends to andincludes the support ring 6. The neck 2 is further characterized by thepresence of the threads 8, which provide a way to fasten a cap for thebottle produced from the preform 1. The body portion 4 is an elongatedand cylindrically shaped structure extending down from the neck 2 andculminating in the rounded end cap 10. The preform thickness 12 willdepend upon the overall length of the preform 1 and the wall thicknessand overall size of the resulting container. It should be noted that asthe terms “neck” and “body” are used herein, in a container that iscolloquially called a “longneck” container, the elongate portion justbelow the support ring, threads, and/or lip where the cap is fastenedwould be considered part of the “body” of the container and not a partof the “neck”.

Referring to FIG. 3, a cross-section of one type of coated preform 20having features in accordance with a preferred embodiment is depicted.The coated preform 20 has a neck portion 2 and a body portion 4 as inthe uncoated preform 1 in FIGS. 1 and 2. The coating layer 22 isdisposed about the entire surface of the body portion 4, terminating atthe bottom of the support ring 6. A coating layer 22 in the embodimentshown in the figure does not extend to the neck portion 2, nor is itpresent on the interior surface 16 of the preform which is preferablymade of an FDA approved material such as PET. The coating layer 22 maycomprise one layer of a single material, one layer of several materialscombined, or several layers of at least two materials. The overallthickness 26 of the preform is equal to the thickness of the initialpreform plus the thickness 24 of the coating layer or layers, and isdependent upon the overall size and desired coating thickness of theresulting container.

FIG. 4 is an enlargement of a wall section of the preform showing themakeup of the coating layers in one embodiment of a preform. The layer110 is the substrate layer of the preform while 112 comprises thecoating layers of the preform. The outer coating layer 116 comprises oneor more layers of material, while 114 comprises the inner coating layer.In preferred embodiments there may be one or more outer coating layers.As shown here, the coated preform has one inner coating layer and twoouter coating layers. Not all preforms of FIG. 4 will be of this type.

Referring to FIG. 5, another embodiment of a coated preform 25 is shownin cross-section. The primary difference between the coated preform 25and the coated preform 20 in FIG. 3 is that the coating layer 22 isdisposed on the support ring 6 of the neck portion 2 as well as the bodyportion 4. Preferably any coating that is disposed on, especially on theupper surface, or above the support ring 6 is made of an FDA approvedmaterial such as PET.

The coated preforms and containers can have layers which have a widevariety of relative thicknesses. In view of the present disclosure, thethickness of a given layer and of the overall preform or container,whether at a given point or over the entire container, can be chosen tofit a coating process or a particular end use for the container.Furthermore, as discussed above in regard to the coating layer in FIG.3, the coating layer in the preform and container embodiments disclosedherein may comprise a single material, a layer of several materialscombined, or several layers of at least two or more materials.

After a coated preform, such as that depicted in FIG. 3, is prepared bya method and apparatus such as those discussed in detail below, it issubjected to a stretch blow-molding process. Referring to FIG. 6, inthis process a coated preform 20 is placed in a mold 28 having a cavitycorresponding to the desired container shape. The coated preform is thenheated and expanded by stretching and by air forced into the interior ofthe preform 20 to fill the cavity within the mold 28, creating a coatedcontainer 30. The blow molding operation normally is restricted to thebody portion 4 of the preform with the neck portion 2 including thethreads, pilfer ring, and support ring retaining the originalconfiguration as in the preform.

Referring to FIG. 7, there is disclosed an embodiment of coatedcontainer 40 in accordance with a preferred embodiment, such as thatwhich might be made from blow molding the coated preform 20 of FIG. 3.The container 40 has a neck portion 2 and a body portion 4 correspondingto the neck and body portions of the coated preform 20 of FIG. 3. Theneck portion 2 is further characterized by the presence of the threads 8which provide a way to fasten a cap onto the container.

When the coated container 40 is viewed in cross-section, as in FIG. 8,the construction can be seen. The coating 42 covers the exterior of theentire body portion 4 of the container 40, stopping just below thesupport ring 6. The interior surface 50 of the container, which is madeof an FDA-approved material, preferably PET, remains uncoated so thatonly the interior surface 50 is in contact with the packaged productsuch as beverages, foodstuffs, or medicines. In one preferred embodimentthat is used as a carbonated beverage container, a 24 gram preform isblow molded into a 16 ounce bottle with a coating ranging from about0.05 to about 0.75 grams, including about 0.1 to about 0.2 grams.

Referring to FIG. 9 there is shown a preferred three-layer preform 76.This embodiment of coated preform is preferably made by placing twocoating layers 80 and 82 on a preform 1 such as that shown in FIG. 1.

Referring to FIG. 10 there is shown a non-limiting flow diagram thatillustrates a preferred process and apparatus. A preferred process andapparatus involves entry of the article into the system 84, dip, spray,or flow coating of the article 86, removal of excess material 88,drying/curing 90, cooling 92, and ejection from the system 94.

Referring to FIG. 11 there is shown a non-limiting flow diagram of oneembodiment of a preferred process wherein the system comprises a singlecoating unit, A, of the type in FIG. 10 which produces a single coatarticle. The article enters the system 84 prior to the coating unit andexits the system 94 after leaving the coating unit.

Referring to FIG. 12 there is shown a non-limiting flow diagram of apreferred process wherein the system comprises a single integratedprocessing line that contains multiple stations 100, 101, 102 whereineach station coats and dries or cures the article thereby producing anarticle with multiple coatings. The article enters the system 84 priorto the first station 100 and exits the system 94 after the last station102. The embodiment described herein illustrates a single integratedprocessing line with three coating units, it is to be understood thatnumbers of coating units above or below are also included.

Referring to FIG. 13 there is shown a non-limiting flow diagram of oneembodiment of a preferred process. In this embodiment, the system ismodular wherein each processing line 107, 108, 109 is self-containedwith the ability to handoff to another line 103, thereby allowing forsingle or multiple coatings depending on how many modules are connectedthereby allowing maximum flexibility. The article first enters thesystem at one of several points in the system 84 or 120. The article canenter 84 and proceed through the first module 107, then the article mayexit the system at 118 or continue to the next module 108 through a handoff mechanism 103 known to those of skill in the art. The article thenenters the next module 108 at 120. The article may then continue on tothe next module 109 or exit the system. The number of modules may bevaried depending on the production circumstances required. Further theindividual coating units 104 105 106 may comprise different coatingmaterials depending on the requirements of a particular production line.The interchangeability of different modules and coating units providesmaximum flexibility.

Referring to FIGS. 14, 15, and 16 there are shown alternate views ofnon-limiting diagrams of one embodiment of a preferred process. In thisembodiment, the top view of a system comprising a single flow coater 86is shown. The preform enters the system 84 and then proceeds to the flowcoater 86 wherein the preform 1 passes through the coating materialwaterfall. The coating material proceeds from the tank or vat 150through the gap 155 in the tank down the angled fluid guide 160 where itforms a waterfall (not illustrated) as it passes onto the preforms. Thegap 155 in the tank may be widened or narrowed to adjust the flow of thematerial. The material is pumped from the reservoir (not illustrated)into the vat or tank at a rate that maintains the coating material levelabove that of the gap 155. Advantageously, this configuration ensures aconstant flow of coating material. The excess amount of material alsodampens any fluid fluctuations due to the cycling of the pump. As thepreform passes out of the coating waterfall, excess material drips offinto the material collection reservoir 170. The coating materialcollector (not illustrated) receives any unused coating waterfall andreturns the material back to the coating tank or vat. The excessmaterial is then removed from the bottom of the preform 88. The preformthen moves toward the drying/curing unit 90 before being ejected fromthe system 94. As shown here, the preforms are allowed to rest beforeejection to cool. The collection reservoir and coating materialcollector preferably empty into the reservoir that feeds the tank or vatso as to allow for reduction of waste from the system.

Referring to FIGS. 17A and 17B there are shown non-limiting views of oneembodiment of a preferred IR drying/curing unit 90. As shown in FIG. 17Athe unit 90 is open. The arrow at the bottom of the unit indicates howthe unit would close. On one side of the processing line there is showna series of ten lamps 200. Below the preforms there is shown an angledreflector 210 which reflects heat towards the bottom of the preforms formore thorough curing. Opposite to the lamps is a semicircular reflector230 which reflects the IR heat back onto the preforms allowing for amore thorough and efficient cure. Reflectors of other shapes and sizesmay also be used.

Referring to FIG. 17B there is an enlarged section detailing the lampplacement in one embodiment of a preferred IR drying/curing unit 90. Thelamps in this embodiment are adjustable 220 and may be moved closer toor farther away from the preform allowing for maximum drying/curingflexibility.

A preferred method and apparatus for making coated articles, morespecifically preforms, is discussed in more detail below.

C. Physical Characteristics of Preferred Coating Materials

The following physical characteristics are described in terms of apreferred material, PET. However, those of skill in the art willunderstand that other suitable substrates, as mentioned previously, maybe used.

The glass transition temperature (Tg) is a property relating to thetransition of a polymer from a glassy form to a plastic form. In a rangeof temperatures above its Tg, a material will become soft enough toallow it to flow readily when subjected to an external force orpressure, yet not so soft that its viscosity is so low that it acts morelike a liquid than a pliable solid. The temperature range above Tg is apreferred temperature range for performing a blow-molding process, asthe material is soft enough to flow under the force of the air blowninto the preform to fit the mold but not so soft that it breaks up orbecomes uneven in texture. Thus, when materials have similar glasstransition temperatures, they will have similar preferred blowingtemperature ranges, allowing the materials to be processed togetherwithout compromising the performance of either material.

In the blow-molding process to produce a bottle from a preform, thepreform is heated to a temperature slightly above the Tg of the preformmaterial so that when air is forced into the preform's interior, it willbe able to flow to fill the mold in which it is placed. If one does notsufficiently heat the preform the preform material will be too hard toflow properly, and would likely crack, craze, or not expand to fill themold. Conversely, if one heats the preform to a temperature well abovethe Tg, the material would likely become so soft that it would not beable to hold its shape or it would crystallize and would processimproperly.

If the material which forms a coating layer has a Tg similar to that ofthe chosen substrate material, it will have a blowing temperature rangesimilar to the substrate. For example, if a PET preform is coated withsuch a material, a blowing temperature can be chosen that allows bothmaterials to be processed within their preferred blowing temperatureranges. If the coating were to have a Tg dissimilar to that of PET, itwould be difficult, if not impossible, to choose a blowing temperaturesuitable for both materials. When coating materials comprise polymershaving a Tg similar to PET (or the chosen substrate material), thecoated preform behaves during blow molding substantially as if it weremade of one material, expanding smoothly and creating a cosmeticallyappealing container with an even thickness and uniform coating of thematerial where it is applied.

The glass transition temperature of PET occurs in a window of about75-85° C., depending upon how the PET has been processed previously.Therefore, the Tg for preferred coating materials to coat PET preferablyrange from about 55 to about 140° C., more preferably from about 90 toabout 110° C., including about 60, 65, 70, 80, 95, 100, 105, 115, 120,and 130. One should note that if the coating is applied to a container,such as a bottle, the Tg of the coating material is greatly diminishedin importance because the need for blow molding is absent.

Another factor which has an impact on the performance of coated preformsduring blow molding is the state of the material. It is preferred thatcoating materials be amorphous rather than crystalline. This is becausematerials in an amorphous state are easier to form into bottles andcontainers by use of a blow molding process than materials in acrystalline state. PET can exist in both crystalline and amorphousforms. However, in certain embodiments of the present invention, it ispreferred that the crystallinity of the PET be minimized and theamorphous state maximized in order to create a semi-crystalline statewhich, among other things, aids interlayer adhesion and in the blowmolding process. In other embodiments, such as when the article coatedis a container such that there is no subsequent blow molding or whencrystallinity is desired, such as for hot-fill containers, havingamorphous substrates and/or coatings is not important, and may even becontraindicated.

Preferred coating materials may have tensile strength and creepresistance similar to PET or the chosen substrate material. If so, theymay act as a structural component of the container, allowing the coatingmaterial to displace some of the polyethylene terephthalate in thepreform without sacrificing preform performance. Similarity in tensilestrength between PET and the coating materials helps the container tohave structural integrity while similarity in creep resistance betweenPET and the coating materials helps the container to retain its shape.Creep resistance relates to the ability of a material to resist changingits shape in response to an applied force. Although certain preferredembodiments may have coatings that provide structural integrity, otherpreferred embodiments may not.

For applications where optical clarity is of importance, preferredcoating materials have an index of refraction similar to that of PET orthe chosen substrate material. When the refractive index of the PET andthe coating material are similar, the preforms and, perhaps moreimportantly, the containers blown therefrom are optically clear and,thus, cosmetically appealing for use as a beverage container whereclarity of the bottle is frequently desired. If, however, the twomaterials have substantially dissimilar refractive indices when they areplaced in contact with each other, the resulting combination may havevisual distortions and may be cloudy or opaque, depending upon thedegree of difference in the refractive indices of the materials.

Polyethylene terephthalate has an index of refraction for visible lightwithin the range of about 1.40 to 1.75, depending upon its physicalconfiguration. When made into preforms, the refractive index ispreferably within the range of about 1.55 to 1.75, and more preferablyin the range of 1.55-1.65. After the preform is made into a bottle, thewall of the final product, may be characterized as a biaxially-orientedfilm since it is subject to both hoop and axial stresses in the blowmolding operation. Blow molded PET generally exhibits a refractive indexwithin the range of about 1.40 to 1.75, usually about 1.55 to 1.75,depending upon the stretch ratio involved in the blow molding operation.For relatively low stretch ratios of about 6: 1, the refractive indexwill be near the lower end, whereas for high stretch ratios, about 10:1,the refractive index will be near the upper end of the aforementionedrange. It will be recognized that the stretch ratios referred to hereinare biaxial stretch ratios resulting from and include the product of thehoop stretch ratio and the axial stretch ratio. For example, in a blowmolding operation in which the final preform is enlarged by a factor of2.5 in the axial direction and a factor of 3.5 diametrically, thestretch ratio will be about 8.75 (2.5×3.5).

Using the designation n_(i) to indicate the refractive index for PET andn_(o) to indicate the refractive index for the coating material, theratio between the values n_(i) and n_(o) is preferably 0.8-1.3, morepreferably 1.0-1.2, most preferably 1.0-1.1. As will be recognized bythose skilled in the art, for the ratio n_(i)/n_(o)=1 the distortion dueto refractive index will be at a minimum, because the two indices areidentical. As the ratio progressively varies from one, however, thedistortion increases progressively.

D. Preferred Coating Materials

In a preferred embodiment, the coating materials comprise thermoplasticepoxy resins (TPEs). A further preferred embodiment includes “phenoxy”resins which are a subset of thermoplastic epoxy resins. Phenoxy resins,as that term is used herein, include a wide variety of materialsincluding those discussed in WO 99/20462. A further subset of phenoxyresins, and thermoplastic epoxy resins, are preferredhydroxy-phenoxyether polymers, of which polyhydroxyaminoether copolymers(PHAE) is a further preferred material. See for example, U.S. Pat. Nos.6,455,116; 6,180,715; 6,011,111; 5,834,078; 5,814,373; 5,464,924; and5,275,853; see also PCT Application Nos. WO 99/48962; WO 99/12995; WO98/29491; and WO 98/14498.

Preferably, the thermoplastic epoxy resins, more specifically thephenoxy resins, used as coating materials in the present inventioncomprise one of the following types:

-   (1) hydroxy-functional poly(amide ethers) having repeating units    represented by any one of the Formulae Ia, Ib or Ic:-   (2) poly(hydroxy amide ethers) having repeating units represented    independently by any one of the Formulae IIa, IIb or IIc:-   (3) amide- and hydroxymethyl-functionalized polyethers having    repeating units represented by Formula III:-   (4) hydroxy-functional polyethers having repeating units represented    by Formula IV:-   (5) hydroxy-functional poly(ether sulfonamides) having repeating    units represented by Formulae Va or Vb:-   (6) poly(hydroxy ester ethers) having repeating units represented by    Formula VI:-   (7) hydroxy-phenoxyether polymers having repeating units represented    by Formula VII:    and-   (8) poly(hydroxyamino ethers) having repeating units represented by    Formula VIII:    wherein each Ar individually represents a divalent aromatic moiety,    substituted divalent aromatic moiety or heteroaromatic moiety, or a    combination of different divalent aromatic moieties, substituted    aromatic moieties or heteroaromatic moieties; R is individually    hydrogen or a monovalent hydrocarbyl moiety; each Ar₁ is a divalent    aromatic moiety or combination of divalent aromatic moieties bearing    amide or hydroxymethyl groups; each Ar₂ is the same or different    than Ar and is individually a divalent aromatic moiety, substituted    aromatic moiety or heteroaromatic moiety or a combination of    different divalent aromatic moieties, substituted aromatic moieties    or heteroaromatic moieties; R₁ is individually a predominantly    hydrocarbylene moiety, such as a divalent aromatic moiety,    substituted divalent aromatic moiety, divalent heteroaromatic    moiety, divalent alkylene moiety, divalent substituted alkylene    moiety or divalent heteroalkylene moiety or a combination of such    moieties; R₂ is individually a monovalent hydrocarbyl moiety; A is    an amine moiety or a combination of different amine moieties; X is    an amine, an arylenedioxy, an arylenedisulfonamido or an    arylenedicarboxy moiety or combination of such moieties; and Ar₃ is    a “cardo” moiety represented by any one of the Formulae:

wherein Y is nil, a covalent bond, or a linking group, wherein suitablelinking groups include, for example, an oxygen atom, a sulfur atom, acarbonyl atom, a sulfonyl group, or a methylene group or similarlinkage; n is an integer from about 10 to about 1000; x is 0.01 to 1.0;and y is 0 to 0.5.

The term “predominantly hydrocarbylene” means a divalent radical that ispredominantly hydrocarbon, but which optionally contains a smallquantity of a heteroatomic moiety such as oxygen, sulfur, imino,sulfonyl, sulfoxyl, and the like.

The hydroxy-functional poly(amide ethers) represented by Formula I arepreferably prepared by contacting an N,N′-bis(hydroxyphenylamido)alkaneor arene with a diglycidyl ether as described in U.S. Pat. Nos.5,089,588 and 5,143,998.

The poly(hydroxy amide ethers) represented by Formula II are prepared bycontacting a bis(hydroxyphenylamido)alkane or arene, or a combination of2 or more of these compounds, such as N,N′-bis(3-hydroxyphenyl)adipamideor N,N′-bis(3-hydroxyphenyl)glutaramide, with an epihalohydrin asdescribed in U.S. Pat. No. 5,134,218.

The amide- and hydroxymethyl-functionalized polyethers represented byFormula III can be prepared, for example, by reacting the diglycidylethers, such as the diglycidyl ether of bisphenol A, with a dihydricphenol having pendant amido, N-substituted amido and/or hydroxyalkylmoieties, such as 2,2-bis(4-hydroxyphenyl)acetamide and3,5-dihydroxybenzamide. These polyethers and their preparation aredescribed in U.S. Pat. Nos. 5,115,075 and 5,218,075.

The hydroxy-functional polyethers represented by Formula IV can beprepared, for example, by allowing a diglycidyl ether or combination ofdiglycidyl ethers to react with a dihydric phenol or a combination ofdihydric phenols using the process described in U.S. Pat. No. 5,164,472.Alternatively, the hydroxy-functional polyethers are obtained byallowing a dihydric phenol or combination of dihydric phenols to reactwith an epihalohydrin by the process described by Reinking, Barnabeo andHale in the Journal of Applied Polymer Science, Vol. 7, p. 2135 (1963).

The hydroxy-functional poly(ether sulfonamides) represented by Formula Vare prepared, for example, by polymerizing an N,N′-dialkyl orN,N′-diaryldisulfonamide with a diglycidyl ether as described in U.S.Pat. No. 5,149,768.

The poly(hydroxy ester ethers) represented by Formula VI are prepared byreacting diglycidyl ethers of aliphatic or aromatic diacids, such asdiglycidyl terephthalate, or diglycidyl ethers of dihydric phenols with,aliphatic or aromatic diacids such as adipic acid or isophthalic acid.These polyesters are described in U.S. Pat. No. 5,171,820.

The hydroxy-phenoxyether polymers represented by Formula VII areprepared, for example, by contacting at least one dinucleophilic monomerwith at least one diglycidyl ether of a cardo bisphenol, such as9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, orphenolphthalimidine or a substituted cardo bisphenol, such as asubstituted bis(hydroxyphenyl)fluorene, a substituted phenolphthalein ora substituted phenolphthalimidine under conditions sufficient to causethe nucleophilic moieties of the dinucleophilic monomer to react withepoxy moieties to form a polymer backbone containing pendant hydroxymoieties and ether, imino, amino, sulfonamido or ester linkages. Thesehydroxy-phenoxyether polymers are described in U.S. Pat. No. 5,184,373.

The poly(hydroxyamino ethers) (“PHAE” or polyetheramines) represented byFormula VIII are prepared by contacting one or more of the diglycidylethers of a dihydric phenol with an amine having two amine hydrogensunder conditions sufficient to cause the amine moieties to react withepoxy moieties to form a polymer backbone having amine linkages, etherlinkages and pendant hydroxyl moieties. These compounds are described inU.S. Pat. No. 5,275,853. For example, polyhydroxyaminoether copolymerscan be made from resorcinol diglycidyl ether, hydroquinone diglycidylether, bisphenol A diglycidyl ether, or mixtures thereof

The phenoxy thermoplastics commercially available from PhenoxyAssociates, Inc., PAPHEN 25068-38-6 as one example, are suitable for usein the present invention. These hydroxy-phenoxyether polymers are thecondensation reaction products of a dihydric polynuclear phenol, such asbisphenol A, and an epihalohydrin and have the repeating unitsrepresented by Formula IV wherein Ar is an isopropylidene diphenylenemoiety. The process for preparing these is described in U.S. Pat. No.3,305,528, incorporated herein by reference in its entirety.

Generally, preferred TPE, including phenoxy and PHAE, coating materialsform stable aqueous based solutions or dispersions. Preferably, thecoating properties of the solutions/dispersions are not adverselyaffected by contact with water. Preferred coating materials range fromabout 10% solids to about 50% solids, including about 15%, 20%, 25%,30%, 35%, 40% and 45%, and ranges encompassing such percentages.Preferably, the coating material used dissolves or disperses in polarsolvents. These polar solvents include, but are not limited to, water,alcohols, and glycol ethers. See, for example, U.S. Pat. Nos. 6,455,116,6,180,715, and 5,834,078 which describe some preferred TPE solutionsand/or dispersions.

One preferred thermoplastic epoxy coating material is apolyhydroxyaminoether copolymer (PHAE), represented by Formula VIII,dispersion or solution. The dispersion or solution, when applied to acontainer or preform, greatly reduces the permeation rate of a varietyof gases through the container walls in a predictable and well knownmanner. One dispersion or latex made thereof comprises 10-30 percentsolids. A PHAE solution/dispersion may be prepared by stirring orotherwise agitating the PHAE in a solution of water with an organicacid, preferably acetic or phosphoric acid, but also including lactic,malic, citric, or glycolic acid and/or mixtures thereof These PHAEsolution/dispersions also include organic acid salts produced by thereaction of the polyhydroxyaminoethers with these acids.

The following PHAE solutions are examples of suitable TPE solutions. Onesuitable material is BLOX® experimental barrier resin, for exampleXU-19061.00 made with phosphoric acid manufactured by Dow ChemicalCorporation. This particular PHAE dispersion is said to have thefollowing typical characteristics: 30% percent solids, a specificgravity of 1.30, a pH of 4, a viscosity of 24 centipoise (Brookfield, 60rpm, LVI, 22° C.), and a particle size of between 1,400 and 1,800angstroms. Other suitable materials include BLOX® 599-29 resins based onresorcinol have also provided superior results as a barrier material.This particular dispersion is said to have the following typicalcharacteristics: 30% percent solids, a specific gravity of 1.2, a pH of4.0, a viscosity of 20 centipoise (Brookfield, 60 rpm, LVI, 22° C.), anda particle size of between 1500 and 2000 angstroms. Other variations ofthe polyhydroxyaminoether chemistry may prove useful such as crystallineversions based on hydroquinone diglycidylethers. Other suitablematerials include polyhydroxyaminoether solutions by Imperial ChemicalIndustries (“ICI,” Ohio, USA) more specifically coded EXP12468 andEXP12468-4B including cross-linked materials which exhibit high chemicalresistance, low blushing and low surface tension. Other suitablesolutions are disclosed in U.S. patent application Ser. No. 10/______,filed ______, 2003, including one based upon BLOX® 5000 resin that is aproprietary material available from ICI, which comprises ICI-codedcomponents PXR-15700, E6039, and F3473, which exhibits goodcross-linking, chemical resistance and does not exhibit excessivefoaming. Other suitable materials include BLOX® 5000 resin dispersionintermediate, BLOX® XUR 588-29, BLOX® 0000 and 4000 series resins. Thesolvents used to dissolve these materials include, but are not limitedto, polar solvents such as alcohols, water, glycol ethers or blendsthereof.

In one embodiment, preferred thermoplastic epoxies are soluble inaqueous acid. A polymer solution/dispersion may be prepared by stirringor otherwise agitating the thermoplastic epoxy in a solution of waterwith an organic acid, preferably acetic or phosphoric acid, but alsoincluding lactic, malic, citric, or glycolic acid and/or mixturesthereof. In a preferred embodiment, the acid concentration in thepolymer solution is preferably in the range of about 5%-20%, includingabout 5%-10% by weight based on total weight. In other preferredembodiments, the acid concentration may be below about 5% or above about20%; and may vary depending on factors such as the type of polymer andits molecular weight. The amount of dissolved polymer in a preferredembodiment ranges from about 0.1% to about 40%. A uniform and freeflowing polymer solution is preferred. In one embodiment a 10% polymersolution is prepared by dissolving the polymer in a 10% acetic acidsolution at 90° C. Then while still hot the solution is diluted with 20%distilled water to give an 8% polymer solution. At higher concentrationsof polymer, the polymer solution tends to be more viscous.

Examples of preferred copolyester coating materials and a process fortheir preparation is described in U.S. Pat. No. 4,578,295 to Jabarin.They are generally prepared by heating a mixture of at least onereactant selected from isophthalic acid, terephthalic acid and their C₁to C₄ alkyl esters with 1,3 bis(2-hydroxyethoxy)benzene and ethyleneglycol. Optionally, the mixture may further comprise one or moreester-forming dihydroxy hydrocarbon and/orbis(4-β-hydroxyethoxyphenyl)sulfone. Especially preferred copolyestercoating materials are available from Mitsui Petrochemical Ind. Ltd.(Japan) as B-010, B-030 and others of this family.

Examples of preferred polyamide coating materials include MXD-6 fromMitsubishi Gas Chemical (Japan). Other preferred polyamide coatingmaterials are blends of polyamide and polyester, including thosecomprising about 1-10% polyester by weight, where the polyester ispreferably PET or a modified PET. The blends may be ordinary blends orthey may be compatibilized with an antioxidant or other material.Examples of such materials include those described in U.S. patentapplication Ser. No. 10/395,899, filed Mar. 21, 2003, which is herebyincorporated by reference in its entirety. Polyamide materials may alsobe used as substrate materials.

Other preferred coating materials include polyethylene naphthalate(PEN), PEN copolyester, and PET/PEN blends. PEN materials can bepurchased from Shell Chemical Company.

E. Additives to Enhance Coating Materials

An advantage of preferred methods disclosed herein are their flexibilityallowing for the use of multiple functional additives. Additives knownby those of ordinary skill in the art for their ability to provideenhanced CO₂ barriers, O₂ barriers, UV protection, scuff resistance,blush resistance, impact resistance and/or chemical resistance may beused.

Preferred additives may be prepared by methods known to those of skillin the art. For example, the additives may be mixed directly with aparticular coating solution/dispersion, they may be dissolved/dispersedseparately and then added to a particular coating solution/dispersion,or they may be combined with a particular coating prior to addition ofthe solvent that forms the solution/dispersion. In addition, in someembodiments, preferred additives may be used alone as a single coatinglayer.

In preferred embodiments, the barrier properties of a coating layer maybe enhanced by the addition of different additives. Additives arepreferably present in an amount up to about 40% of the coatingsolution/dispersion, also including up to about 30%, 20%, 10%, 5% and 1%of the coating solution/dispersion. Further, additives are preferablystable in aqueous conditions. For example, derivatives of resorcinal(m-dihydroxybenzene) may be used in conjunction with coating materials.The higher the resorcinol content the greater the barrier properties ofthe coating. Another additive that may be used are nanoparticles ornanoparticular materials. These nanoparticles are tiny particles ofmaterials which enhance the barrier properties of a material by creatinga more tortuous path for migrating oxygen or carbon dioxide. Onepreferred type of nanoparticular material is a microparticularclay-based product available from Southern Clay Products.

In preferred embodiments, the UV protection properties of the coatingmay be enhanced by the addition of different additives. In a preferredembodiment, the UV protection coating material used provides UVprotection up to about 350 nm or greater, preferably about 370 nm orgreater, more preferably about 400 nm or greater. The UV protectionmaterial may be used as an additive with layers providing additionalfunctionality or applied separately as a single coat. Preferablyadditives providing enhanced UV protection are present in the coatingsolution/dispersion from about 1 to 20%, but also including about 3%,5%, 10%, and 15%. Preferably the UV protection material is added in aform that is compatible with aqueous based solutions/dispersions. Forexample, a preferred UV protection material is Milliken UV390A clearshield. UV390A is an oily liquid for which mixing is aided by firstblending the liquid with water, preferably in roughly equal parts byvolume. This blend is then added to the TPE solution, for example, BLOX®599-29, and agitated. The resulting solution contains about 10% UV390Aand provides UV protection up to 400 nm when applied to a PET preform.As previously described, in another embodiment the UV390A solution isapplied as a single coating.

In preferred embodiments, CO₂ scavenging properties can be added to thecoating. In one preferred embodiment such properties are achieved byincluding an active amine which will react with CO₂ forming a high gasbarrier salt. This salt will then act as a passive CO₂ barrier. Theactive amine may be an additive or it may be one or more moieties in thethermoplastic resin material of one or more layers.

In preferred embodiments, O₂ scavenging properties can be added to thecoating by including O₂ scavengers such as anthroquinone and othersknown in the art. In other embodiments, these O₂ scavengers may also beused alone as a separate coating. These O₂ scavenging materials mustfirst be activated by UV which can be done prior to the drying/curingprocess.

In another preferred embodiment, a top coat is applied to providechemical resistance to harsher chemicals. Preferably these top coats areaqueous based polyesters or acrylics which are optionally partially orfully cross linked. A preferred aqueous based polyester is polyethyleneterephthalate, however other polyesters may also be used. A preferredaqueous based acrylic is ICI PXR 14100 Carboxyl Latex.

A preferred aqueous based polyester resin is described in U.S. Pat. No.4,977,191 (Salsman), incorporated herein by reference. Morespecifically, U.S. Pat. No. 4,977,191 describes an aqueous basedpolyester resin, comprising a reaction product of 20-50% by weight ofwaste terephthalate polymer, 10-40% by weight of at least one glycol an5-25% by weight of at least one oxyalkylated polyol.

Another preferred aqueous based polymer is a sulfonated aqueous basedpolyester resin composition as described in U.S. Pat. No. 5,281,630(Salsman), herein incorporated by reference. Specifically, U.S. Pat. No.5,281,630 describes an aqueous suspension of a sulfonated water-solubleor water dispersible polyester resin comprising a reaction product of20-50% by weight terephthalate polymer, 10-40% by weight at least oneglycol and 5-25% by weight of at least one oxyalkylated polyol toproduce a prepolymer resin having hydroxyalkyl functionality where theprepolymer resin is further reacted with about 0.10 mole to about 0.50mole of alpha, beta-ethylenically unsaturated dicarboxylic acid per 100g of prepolymer resin and a thus produced resin, terminated by a residueof an alpha, beta-ethylenically unsaturated dicarboxylic acid, isreacted with about 0.5 mole to about 1.5 mole of a sulfite per mole ofalpha, beta-ethylenically unsaturated dicarboxylic acid residue toproduce a sulfonated-terminated resin.

Yet another preferred aqueous based polymer is the coating described inU.S. Pat. No. 5,726,277 (Salsman), incorporated herein by reference.Specifically, U.S. Pat. No. 5,726,277 describes coating compositionscomprising a reaction product of at least 50% by weight of wasteterephthalate polymer and a mixture of glycols including an oxyalkylatedpolyol in the presence of a glycolysis catalyst wherein the reactionproduct is further reacted with a difunctional, organic acid and whereinthe weight ratio of acid to glycols in is the range of 6:1 to 1:2.

While the above examples are provided as preferred aqueous based polymercoating compositions, other aqueous based polymers are suitable for usein the products and methods describe herein. By way of example only, andnot meant to be limiting, further suitable aqueous based compositionsare described in U.S. Pat. No. 4,104,222 (Date, et al.), incorporatedherein by reference. U.S. Pat. No. 4,104,222 describes a dispersion of alinear polyester resin obtained by mixing a linear polyester resin witha higher alcohol/ethylene oxide addition type surface-active agent,melting the mixture and dispersing the resulting melt by pouring it intoan aqueous solution of an alkali under stirring Specifically, thisdispersion is obtained by mixing a linear polyester resin with asurface-active agent of the higher alcohol/ethylene oxide addition type,melting the mixture, and dispersing the resulting melt by pouring itinto an aqueous solution of an alkanolamine under stirring at atemperature of 70-95° C., said alkanolamine being selected from thegroup consisting of monoethanolamine, diethanolamine, triethanolamine,monomethylethanolamine, monoethylethanolamine, diethylethanolamine,propanolamine, butanolamine, pentanolamine, N-phenylethanolamine, and analkanolamine of glycerin, said alkanolamine being present in the aqueoussolution in an amount of 0.2 to 5 weight percent, said surface-activeagent of the higher alcohol/ethylene oxide addition type being anethylene oxide addition product of a higher alcohol having an alkylgroup of at least 8 carbon atoms, an alkyl-substituted phenol or asorbitan monoacylate and wherein said surface-active agent has an HLBvalue of at least 12.

Likewise, by example, U.S. Pat. No. 4,528,321 (Allen) discloses adispersion in a water immiscible liquid of water soluble or waterswellable polymer particles and which has been made by reverse phasepolymerization in the water immiscible liquid and which includes anon-ionic compound selected from C₄₋₁₂ alkylene glycol monoethers, theirC₁₋₄ alkanoates, C₆₋₁₂ polyakylene glycol monoethers and their C₁₋₄alkanoates.

The coating materials may be cross-linked to enhance thermal stabilityof coatings for hot fill applications. Inner layers may compriselow-cross linking materials while outer layers may comprise highcrosslinking materials or other suitable combinations. For example, theinner coating on the PET surface may utilize non or low cross-linkedmaterial, such as the BLOX® 599-29, and the outer coat may utilizematerial, such as EXP 12468-4B, capable of cross linking to ensuremaximum adhesion to the PET. Suitable additives capable of cross linkingmay be added to the coating layer. Suitable cross linkers can be chosendepending upon the chemistry and functionality of the resin to whichthey are added. For example, amine cross linkers may be useful forcrosslinking resins comprising epoxide groups. Preferably cross linkingadditives, if present, are present in an amount of about 1% to 10% ofthe coating solution/dispersion, preferably about 1% to 5%, alsoincluding 2%, 3%, 4%, 6%, 7%, 8%, and 9%.

In some embodiments, the coating material solutions or dispersions formfoam and/or bubbles which can interfere with the coating process. Oneway to avoid this interference, is to add anti-foam/bubble agents to thecoating solution/dispersion. Suitable anti-foam agents include, but arenot limited to, nonionic surfactants, alkylene oxide based materials,siloxane based materials, and ionic surfactants. Preferably anti-foamagents, if present, are present in an amount of about 0.01% to about0.3% of the coating solution/dispersion, preferably about 0.01% to about0.2%, but also including about 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%,0.08%, 0.09%, 0.1%, 0.25%, and ranges encompassing these amounts.

An advantage of the present invention is the ability to handle manytypes of additives and coatings in an aqueous based system. This makesthe present invention easy to use and economical as compared to othersystems. For example, since the present invention is aqueous based,there is no need for expensive systems to handle VOC's used in othersystems such as epoxy thermosets. In addition, most of the solvents cancontact human skin without irritation allowing for ease of use inmanufacturing.

F. Preferred Articles

Generally, preferred articles herein include preforms or containershaving one or more coating layers. The coating layer or layerspreferably provide some functionality such as barrier protection, UVprotection, impact resistance, scuff resistance, blush resistance,chemical resistance, antimicrobial properties, and the like. The layersmay be applied as multiple layers, each layer having one or morefunctional characteristics, or as a single layer containing one or morefunctional components. The layers are applied sequentially with eachcoating layer being partially or fully dried/cured prior to the nextcoating layer being applied.

A preferred substrate is a PET preform or container as described above.However, other substrate materials may also be utilized. Other suitablesubstrate materials include, but are not limited to, polyesters,polypropylene, polyethylene, polycarbonate, polyamides and acrylics.

For example, in one multiple layer article, the inner layer is a primeror base coat having functional properties for enhanced adhesion to PET,O₂ scavenging, UV resistance and passive barrier and the one or moreouter coatings provide passive barrier and scuff resistance. In thedescriptions herein with regard to coating layers, inner is taken asbeing closer to the substrate and outer is taken as closer to theexterior surface of the container. Any layers between inner and outerlayers are generally described as “intermediate” or “middle”. In otherembodiments, multiple coated articles comprise an inner coating layercomprising an O₂ scavenger, an intermediate active UV protection layer,followed by an outer layer of the partially or highly cross-linkedmaterial. In another embodiment, multiple coated preforms comprise aninner coating layer comprising an O₂ scavenger, an intermediate CO₂scavenger layer, an intermediate active UV protection layer, followed byan outer layer of partially or highly cross-linked material. Thesecombinations provide a hard increased cross linked coating that issuitable for carbonated beverages such as beer. In another embodimentuseful for carbonated soft drinks, the inner coating layer is a UVprotection layer followed by an outer layer of cross linked material.Although the above embodiments have been described in connection withparticular beverages, they may be used for other purposes and otherlayer configurations may be used for the referenced beverages.

In a related embodiment, the final coating and drying of the preformprovides scuff resistance to the surface of the preform and finishedcontainer in that the solution or dispersion contains diluted orsuspended paraffin or wax, slipping agent, polysilane or low molecularweight polyethylene to reduce the surface tension of the container.

G. Methods and Apparatus for Preparation of Coated Articles

Once suitable coating materials are chosen, the preform is preferablycoated in a manner that promotes adhesion between the two materials.Although the discussion which follows is in terms of preforms, suchdiscussion should not be taken as limiting, in that the methods andapparatus described may be applied or adapted for containers and otherarticles. Generally, adherence between coating materials and the preformsubstrate increases as the surface temperature of the preform increases.Therefore it is preferable to perform coating on a heated preform,although preferred coating materials will adhere to the preform at roomtemperature.

Plastics generally, and PET preforms specifically, have staticelectricity that results in the preforms attracting dust and gettingdirty quickly. In a preferred embodiment the preforms are taken directlyfrom the injection-molding machine and coated, including while stillwarm. By coating the preforms immediately after they are removed fromthe injection-molding machine, not only is the dust problem avoided, itis believed that the warm preforms enhance the coating process. However,the methods also allow for coating of preforms that are stored prior tocoating. Preferably, the preforms are substantially clean, howevercleaning is not necessary.

In a preferred embodiment an automated system is used. A preferredmethod involves entry of the preform into the system, dip, spray, orflow coating of the preform, optional removal of excess material,drying/curing, cooling, and ejection from the system. The system mayalso optionally include a recycle step. In one embodiment the apparatusis a single integrated processing line that contains two or more dip,flow, or spray coating units and two or more curing/drying units thatproduce a preform with multiple coatings. In another embodiment, thesystem comprises one or more coating modules. Each coating modulecomprises a self-contained processing line with one or more dip, flow,or spray coating units and one or more curing/drying units. Depending onthe module configuration, a preform may receive one or more coatings.For example, one configuration may comprise three coating moduleswherein the preform is transferred from one module to the next, inanother configuration, the same three modules may be in place but thepreform is transferred from the first to the third module skipping thesecond. This ability to switch between different module configurationsallows for flexibility. In a further preferred embodiment either themodular or the integrated systems may be connected directly to a preforminjection-molding machine and/or a blow-molding machine. The injectionmolding machine prepares preforms for use in the present invention.

The following describes a preferred embodiment of a coating system thatis fully automated. This system is described in terms of currentlypreferred materials, but it is understood by one of ordinary skill inthe art that certain parameters will vary depending on the materialsused and the particular physical structure of the desired end-productpreform. This method is described in terms of producing coated 24 grampreforms having about 0.05 to about 0.75 total grams of coating materialdeposited thereon, including about 0.07, 0.09, 0.10, 0.15, 0.20, 0.25,0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, and 0.70 grams. In themethod described below, the coating solution/dispersion is at a suitabletemperature and viscosity to deposit about 0.06 to about 0.20 grams ofcoating material per coating layer on a 24 gram preform, also includingabout 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16. 0.17,0.18, and 0.19 grams per coating layer on a 24 gram preform. Preferreddeposition amounts for articles of varying sizes may be scaled accordingto the increase or decrease in surface area as compared to a 24 grampreform. Accordingly, articles other than 24 gram preforms may falloutside of the ranges stated above. Furthermore, in some embodiments, itmay be desired to have a single layer or total coating amount on a 24gram preform that lies outside of the ranges stated above.

The apparatus and methods may also be used for other similarly sizedpreforms and containers, or may adapted for other sizes of articles aswill be evident to those skilled in the art in view of the discussionwhich follows. Currently preferred coating materials include, TPEs,preferably phenoxy type resins, more preferably PHAEs, including theBLOX resins noted supra. These materials and methods are given by way ofexample only and are not intended to limit the scope of the invention inany way.

1. Entry into the System

The preforms are first brought into the system. An advantage of onepreferred method is that ordinary preforms such as those normally usedby those of skill in the art may be used. For example, 24 gram monolayerpreforms of the type in common use to make 16 ounce bottles can be usedwithout any alteration prior to entry into the system. In one embodimentthe system is connected directly to a preform injection molding machineproviding warm preforms to the system. In another embodiment storedpreforms are added to the system by methods well known to those skilledin the art including those which load preforms into an apparatus foradditional processing. Preferably the stored preforms are pre-warmed toabout 100° F. to about 130° F., including about 120° F., prior to entryinto the system. The stored preforms are preferably clean, althoughcleaning is not necessary. PET preforms are preferred, however otherpreform and container substrates can be used. Other suitable articlesubstrates include, but are not limited to, various polymers such aspolyesters, polyolefins, including polypropylene and polyethylene,polycarbonate, polyamides, including nylons, or acrylics.

2. Dip, Spray, or Flow Coating

Once a suitable coating material is chosen, it can be prepared and usedfor either dip, spray, or flow coating. The material preparation isessentially the same for dip, spray, and flow coating. The coatingmaterial comprises a solution/dispersion made from one or more solventsinto which the resin of the coating material is dissolved and/orsuspended.

The temperature of the coating solution/dispersion can have a drasticeffect on the viscosity of the solution/dispersion. As temperatureincreases, viscosity decreases and vice versa. In addition, as viscosityincreases the rate of material deposition also increases. Thereforetemperature can be used as a mechanism to control deposition. In oneembodiment using flow coating, the temperature of thesolution/dispersion is maintained in a range cool enough to minimizecuring of the coating material but warm enough to maintain a suitableviscosity. In one embodiment, the temperature is about 60° F.-80° F.,including about 70° F. In some cases, solutions/dispersions that may betoo viscous to use in spray or flow coating may be used in dip coating.Similarly, because the coating material may spend less time at anelevated temperature in spray coating, higher temperatures than would berecommended for dip or flow coating because of curing problems may beutilized in spray coating. In any case, a solution or dispersion may beused at any temperature wherein it exhibits suitable properties for theapplication. In preferred embodiments, a temperature control system isused to ensure constant temperature of the coating solution/dispersionduring the application process. In certain embodiments, as the viscosityincreases, the addition of water may decrease the viscosity of thesolution/dispersion. Other embodiments may also include a water contentmonitor and/or a viscosity monitor that provides a signal when viscosityfalls outside a desired range and/or which automatically adds water orother solvent to achieve viscosity within a desired range.

In a preferred embodiment, the solution/dispersion is at a suitabletemperature and viscosity to deposit about 0.06 to about 0.2 grams percoat on a 24 gram preform, also including about 0.07, 0.08, 0.09, 0.1,0.11, 0.12, 0.13, 0.14, 0.15, 0.16. 0.17, 0.18, and 0.19 grams percoating layer on a 24 gram preform. Preferred deposition amounts forarticles of varying sizes may be scaled according to the increase ordecrease in surface area as compared to a 24 gram preform. Accordingly,articles other than 24 gram preforms may fall outside of the rangesstated above. Furthermore, in some embodiments, it may be desired tohave a single layer on a 24 gram preform that lies outside of the rangesstated above.

In one embodiment, coated preforms produced from dip, spray, or flowcoating are of the type seen in FIG. 3. The coating 22 is disposed onthe body portion 4 of the preform and does not coat the neck portion 2.The interior of the coated preform 16 is preferably not coated. In apreferred embodiment this is accomplished through the use of a holdingmechanism comprising an expandable collet or grip mechanism that isinserted into the preform combined with a housing surrounding theoutside of the neck portion of the preform. The collet expands therebyholding the preform in place between the collet and the housing. Thehousing covers the outside of the neck including the threading, therebyprotecting the inside of the preform as well as the neck portion fromcoating.

In preferred embodiments, coated preforms produced from dip, spray, orflow coating produce a finished product with substantially nodistinction between layers. Further, in dip and flow coating procedures,it has been found that the amount of coating material deposited on thepreform decreases slightly with each successive layer.

A. Dip Coating

In a preferred embodiment, the coating is applied through a dip coatingprocess. The preforms are dipped into a tank or other suitable containerthat contains the coating material. The dipping of the preforms into thecoating material can be done manually by the use of a retaining rack orthe like, or it may be done by a fully automated process. Although theapparatus shown in FIG. 14 depicts one embodiment of an automated flowcoating unit, in certain embodiments utilizing automated dip coating,the position of the flow coater 86 would represent the positioning ofthe dip coating tank or other suitable container containing the coatingmaterial.

In a preferred embodiment, the preforms are rotating while being dippedinto the coating material. The preform preferably rotates at a speed ofabout 30-80 RPM, more preferably about 40 RPM, but also including 50,60, and 70 RPM. This allows for thorough coating of the preform. Otherspeeds may be used, but preferably not so high as to cause loss ofcoating material due to centrifugal forces.

The preform is preferably dipped for a period of time sufficient toallow for thorough coverage of the preform. Generally, this ranges fromabout 0.25 to about 5 seconds although times above and below this rangeare also included. Without wishing to be bound to any theory, it appearsthat longer residence time does not provide any added coating benefit.

In determining the dipping time and therefore speed, the turbidity ofthe coating material should also be considered. If the speed is too highthe coating material may become wavelike and splatter causing coatingdefects. Another consideration is that many coating material solutionsor dispersions form foam and/or bubbles which can interfere with thecoating process. To avoid this interference, the dipping speed ispreferably chosen to avoid excessive agitation of the coating material.If necessary anti-foam/bubble agents may be added to the coatingsolution/dispersion.

B. Spray Coating

In a preferred embodiment, the coating is applied through a spraycoating process. The preforms are sprayed with a coating material thatis in fluid connection with a tank or other suitable container thatcontains the coating material. The spraying of the preforms with thecoating material can be done manually with the use of a retaining rackor the like, or it may be done by a fully automated process. Althoughthe apparatus shown in FIG. 14 depicts one embodiment of an automatedflow coating unit, in certain embodiments utilizing automated spraycoating, the position of the flow coater 86 would represent thepositioning of the spray coating apparatus.

In a preferred embodiment, the preforms are rotating while being sprayedwith the coating material. The preform preferably rotates at a speed ofabout 30-80 RPM, more preferably about 40 RPM, but also including about50, 60, and 70 RPM. Preferably, the preform rotates at least about 360°while proceeding through the coating spray. This allows for thoroughcoating of the preform. The preform may, however, remain stationarywhile spray is directed at the preform.

The preform is preferably sprayed for a period of time sufficient toallow for thorough coverage of the preform. The amount of time requiredfor spraying depends upon several factors, which may include thespraying rate (volume of spray per unit time), the area encompassed bythe spray, and the like.

The coating material is contained in a tank or other suitable containerin fluid communication with the production line. Preferably a closedsystem is used in which unused coating material is recycled. In oneembodiment, this may be accomplished by collecting any unused coatingmaterial in a coating material collector which is in fluid communicationwith the coating material tank. Many coating material solutions ordispersions form foam and/or bubbles which can interfere with thecoating process. To avoid this interference, the coating material ispreferably removed from the bottom or middle of the tank. Additionally,it is preferable to decelerate the material flow prior to returning tothe coating tank to further reduce foam and/or bubbles. This can be doneby means known to those of skill in the art. If necessaryanti-foam/bubble agents may be added to the coating solution/dispersion.

In determining the spraying time and associated parameters such asnozzle size and configuration, the properties of the coating materialshould also be considered. If the speed is too high and/or the nozzlesize incorrect, the coating material may splatter causing coatingdefects. If the speed is too slow or the nozzle size incorrect, thecoating material may be applied in a manner thicker than desired.Suitable spray apparatus include those sold by Nordson Corporation(Westlake, Ohio). Another consideration is that many coating materialsolutions or dispersions form foam and/or bubbles which can interferewith the coating process. To avoid this interference, the sprayingspeed, nozzle used and fluid connections are preferably chosen to avoidexcessive agitation of the coating material. If necessaryanti-foam/bubble agents may be added to the coating solution/dispersion.

C. Flow Coating

In a preferred embodiment, the coating is applied through a flow coatingprocess. The object of flow coating is to provide a sheet of material,similar to a falling shower curtain or waterfall, that the preformpasses through for thorough coating. Advantageously, preferred methodsof flow coating allow for a short residence time of the preform in thecoating material. The preform need only pass through the sheet a periodof time sufficient to coat the surface of the preform. Without wishingto be bound to any theory, it appears that longer residence time doesnot provide any added coating benefit.

Referring to FIGS. 14, 15, and 16 there are shown alternate views ofnon-limiting diagrams of one embodiment of a preferred flow coatingprocess. In this embodiment, the top view of a system comprising asingle flow coater 86 is shown. The preform enters the system 84 andthen proceeds to the flow coater 86 wherein the preform 1 passes throughthe coating material waterfall (not illustrated). The coating materialproceeds from the tank or vat 150 through the gap 155 in the tank downthe angled fluid guide 160 where it forms a waterfall as it passes ontothe preforms. Other embodiments may have fluid guides that aresubstantially horizontal. The gap 155 in the tank 150 may be widened ornarrowed to adjust the flow of the material. The material is pumped fromthe reservoir (not illustrated) into the vat or tank 150 at a rate thatmaintains the coating material level above that of the gap 155.Advantageously, this configuration ensures a constant flow of coatingmaterial. The excess amount of material also dampens any fluidfluctuations due to the cycling of the pump.

In order to provide an even coating the preform is preferably rotatingwhile it proceeds through the sheet of coating material. The preformpreferably rotates at a speed of about 30-80 RPM, more preferably about40 RPM, but also including 50, 60, and 70 RPM. Preferably, the preformrotates at least about two full rotations or 720° while being proceedingthrough the sheet of coating material. In one preferred embodiment, thepreform is rotating and placed at an angle while it proceeds through thecoating material sheet. The angle of the preform is preferably acute tothe plane of the coating material sheet. This advantageously allows forthorough coating of the preform without coating the neck portion orinside of the preform. In another preferred embodiment, the preform 1 asshown in FIG. 16 is vertical, or perpendicular to the floor, while itproceeds through the coating material sheet. It has been found that asthe coating material sheet comes into contact with the preform the sheettends to creep up the wall of the preform from the initial point ofcontact. One of skill in the art can control this creep effect byadjusting parameters such as the flow rate, coating material viscosity,and physical placement of the coating sheet material relative to thepreform. For example, as the flow increases the creep effect may alsoincrease and possibly cause the coating material to coat more of thepreform than is desirable. As another example, by decreasing the angleof the perform relative to the coating material sheet, coating thicknessmay be adjusted to retain more material at the center or body of theperform as the angle adjustment decreases the amount of material removedor displaced to the bottom of the preform by gravity. The ability tomanipulate this creep effect advantageously allows for thorough coatingof the preform without coating the neck portion or inside of thepreform.

The coating material is contained in a tank or other suitable containerin fluid communication with the production line in a closed system. Itis preferable to recycle any unused coating material. In one embodiment,this may be accomplished by collecting the returning waterfall flowstream in a coating material collector which is in fluid communicationwith the coating material tank. Many coating material solutions ordispersions form foam and/or bubbles which can interfere with thecoating process. To avoid this interference, the coating material ispreferably removed from the bottom or middle of the tank. Additionally,it is preferable to decelerate the material flow prior to returning tothe coating tank to further reduce foam and/or bubbles. This can be doneby means known to those of skill in the art. If necessaryanti-foam/bubble agents may be added to the coating solution/dispersion.

In choosing the proper flow rate of coating materials, several variablesshould be considered to provide proper sheeting, including coatingmaterial viscosity, flow rate velocity, length and diameter of thepreform, line speed and preform spacing.

The flow rate velocity determines the accuracy of the sheet of material.If the flow rate is too fast or too slow, the material may notaccurately coat the preforms. When the flow rate is too fast, thematerial may splatter and overshoot the production line causingincomplete coating of the preform, waste of the coating material, andincreased foam and/or bubble problems. If the flow rate is too slow thecoating material may only partially coat the preform.

The length and the diameter of the preform to be coated should also beconsidered when choosing a flow rate. The sheet of material shouldthoroughly cover the entire preform, therefore flow rate adjustments maybe necessary when the length and diameter of preforms are changed.

Another factor to consider is the spacing of the preforms on the line.As the preforms are run through the sheet of material a so-called wakeeffect may be observed. If the next preform passes through the sheet inthe wake of the prior preform it may not receive a proper coating.Therefore it is important to monitor the speed and center line of thepreforms. The speed of the preforms will be dependant on the throughputof the specific equipment used.

3. Removal of Excess Material

Advantageously preferred methods provide such efficient deposition thatvirtually all of the coating on the preform is utilized (i.e. there isvirtually no excess material to remove). However there are situationswhere it is necessary to remove excess coating material after thepreform is coated by dip, spray or flow methods. Preferably, therotation speed and gravity will work together to normalize the sheet onthe preform and remove any excess material. Preferably, preforms areallowed to normalize for about 5 to about 15 seconds, more preferablyabout 10 seconds. If the tank holding the coating material is positionedin a manner that allows the preform to pass over the tank after coating,the rotation of the preform and gravity may cause some excess materialto drip off of the preform back into the coating material tank. Thisallows the excess material to be recycled without any additional effort.If the tank is situated in a manner where the excess material does notdrip back into the tank, other suitable means of catching the excessmaterial and returning it to be reused, such as a coating materialcollector or reservoir in fluid communication with the coating tank orvat, may be employed.

Where the above methods are impractical due to production circumstancesor insufficient, various methods and apparatus, such as a drip remover88, known to those skilled in the art may be used to remove the excessmaterial. See e.g. FIGS. 14, 15, and 16. For example, suitable dripremovers include one or more of the following: a wiper, brush, spongeroller, air knife or air flow, which may be used alone or in conjunctionwith each other. Further, any of these methods may be combined with therotation and gravity method described above. Preferably any excessmaterial removed by these methods is recycled for further use.

4. Drying and Curing

After the preform 1 has been coated and any excess material removed 88,the coated preform is then dried and cured 90. The drying and curingprocess is preferably performed by infrared (IR) heating 90. See FIGS.14, 15, 17A, and 17B. In one embodiment, a 1000 W quartz IR lamp 200 isused as the source. A preferred source is a General Electric Q1500 T3/CLQuartzline Tungsten-Halogen lamp. This particular source and equivalentsources may be purchased commercially from any of a number of sourcesincluding General Electric and Phillips. The source may be used at fullcapacity, or it may be used at partial capacity such as at about 50%,about 65%, about 75% and the like. Preferred embodiments may use asingle lamp or a combination of multiple lamps. For example, six IRlamps may be used at 70% capacity.

Preferred embodiments may also use lamps whose physical orientation withrespect to the preform is adjustable. As shown in FIGS. 17A and 17B, thelamp position 200 may be adjusted 220 to position the lamp closer to orfarther away from the preform. For example, in one embodiment withmultiple lamps, it may be desirable to move one or more of the lampslocated below the bottom of the preform closer to the preform. Thisadvantageously allows for thorough curing of the bottom of the preform.Embodiments with adjustable lamps may also be used with preforms ofvarying widths. For example, if a preform is wider at the top than atthe bottom, the lamps may be positioned closer to the preform at thebottom of the preform to ensure even curing. The lamps are preferablyoriented so as to provide relatively even illumination of all surfacesof the coating.

In other embodiments reflectors are used in combination with IR lamps toprovide thorough curing. In preferred embodiments lamps 200 arepositioned on one side of the processing line while one or morereflectors 210 230 are located on the opposite side of or below theprocessing line. This advantageously reflects the lamp output back ontothe preform allowing for a more thorough cure. More preferably anadditional reflector 210 is located below the preform to reflect heatfrom the lamps upwards towards the bottom of the preform. Thisadvantageously allows for thorough curing of the bottom of the preform.In other preferred embodiments various combinations of reflectors may beused depending on the characteristics of the articles and the IR lampsused. More preferably reflectors are used in combination with theadjustable IR lamps described above.

FIG. 17 depicts a view of one non-limiting embodiment of a preferred IRdrying/curing unit. On one side of the processing line there is shown aseries of lamps 200. Below the preforms there is shown an angledreflector 210 which reflects heat towards the bottom of the preforms formore thorough curing. Opposite to the lamps is a semicircular reflector230 which reflects the IR heat back onto the preforms allowing for amore thorough and efficient cure. FIG. 17B is an enlarged section of thelamp which demonstrates an embodiment where the lamp placement isadjustable 220. The lamps may be moved closer to or farther away fromthe preform allowing for maximum drying/curing flexibility.

In addition, the use of infrared heating allows for the thermoplasticepoxy (for example PHAE) coating to dry without overheating the PETsubstrate and can be used during preform heating prior to blow molding,thus making for an energy efficient system. Also, it has been found thatuse of IR heating can reduce blushing and improve chemical resistance.

Although this process may be performed without additional air, it ispreferred that IR heating be combined with forced air. The air used maybe hot, cold, or ambient. The combination of IR and air curing providesthe unique attributes of superior chemical, blush, and scuff resistanceof preferred embodiments. Further, without wishing to be bound to anyparticular theory, it is believed that the coating's chemical resistanceis a function of crosslinking and curing. The more thorough the curing,the greater the chemical resistance.

In determining the length of time necessary to thoroughly dry and curethe coating several factors such as coating material, thickness ofdeposition, and preform substrate should be considered. Differentcoating materials cure faster or slower than others. Additionally, asthe degree of solids increases, the cure rate decreases. Generally, forIR curing, 24 gram preforms with about 0.05 to about 0.75 grams ofcoating material the curing time is about 5 to 60 seconds, althoughtimes above and below this range may also be used.

Another factor to consider is the surface temperature of the preform asit relates to the glass transition temperature (T_(g)) of the substrateand coating materials. Preferably the surface temperature of the coatingexceeds the T_(g) of the coating materials without heating the substrateabove the substrate T_(g) during the curing/drying process. Thisprovides the desired film formation and/or crosslinking withoutdistorting the preform shape due to overheating the substrate. Forexample, where the coating material has a higher T_(g) than the preformsubstrate material, the preform surface is preferably heated to atemperature above the T_(g) of the coating while keeping the substratetemperature at or below the substrate T_(g). One way of regulating thedrying/curing process to achieve this balance is to combine IR heatingand air cooling, although other methods may also be used.

An advantage of using air in addition to IR heating is that the airregulates the surface temperature of the preform thereby allowingflexibility in controlling the penetration of the radiant heat. If aparticular embodiment requires a slower cure rate or a deeper IRpenetration, this can be controlled with air alone, time spent in the IRunit, or the IR lamp frequency. These may be used alone or incombination.

Preferably, the preform rotates while proceeding through the IR heater.The preform preferably rotates at a speed of about 30-80 RPM, morepreferably about 40 RPM. If the rotation speed is too high, the coatingwill spatter causing uneven coating of the preform. If the rotationspeed is too low, the preform dries unevenly. More preferably, thepreform rotates at least about 360° while proceeding through the IRheater. This advantageously allows for thorough curing and drying.

In other preferred embodiments, Electron Beam Processing may be employedin lieu of IR heating or other methods. Electron Beam Processing (EBP)has not been used for curing of polymers used for and in conjunctionwith injection molded performs and containers primarily due to its largesize and relatively high cost. However recent advances in thistechnology, are expected to give rise to smaller less expensivemachines. EBP accelerators are typically described in terms of theirenergy and power. For example, for curing and crosslinking of food filmcoatings, accelerators with energies of 150-500 keV are typically used.

EBP polymerization is a process in which several individual groups ofmolecules combine together to form one large group (polymer). When asubstrate or coating is exposed to highly accelerated electrons, areaction occurs in which the chemical bonds in the material are brokenand a new, modified molecular structure is formed. This polymerizationcauses significant physical changes in the product, and may result indesirable characteristics such as high gloss and abrasion resistance.EBP can be a very efficient way to initiate the polymerization processin many materials.

Similar to EBP polymerization, EBP crosslinking is a chemical reaction,which alters and enhances the physical characteristics of the materialbeing treated. It is the process by which an interconnected network ofchemical bonds or links develop between large polymer chains to form astronger molecular structure. EBP may be used to improve thermal,chemical, barrier, impact, wear and other properties of inexpensivecommodity thermoplastics. EBP of crosslinkable plastics can yieldmaterials with improved dimensional stability, reduced stress cracking,higher set temperatures, reduced solvent and water permeability andimproved thermomechanical properties.

The effect of the ionizing radiation on polymeric material is manifestedin one of three ways: (1) those that are molecular weight-increasing innature (crosslinking); (2) those that are molecular weight-reducing innature (scissioning); or (3), in the case of radiation resistantpolymers, those in which no significant change in molecular weight isobserved. Certain polymers may undergo a combination of (1) and (2).During irradiation, chain scissioning occurs simultaneously andcompetitively with crosslinking, the final result being determined bythe ratio of the yields of these reactions. Polymers containing ahydrogen atom at each carbon atom predominantly undergo crosslinking,while for those polymers containing quaternary carbon atoms and polymersof the —CX₂—CX₂— type (when X=halogen), chain scissioning predominates.Aromatic polystyrene and polycarbonate are relatively resistant to EBP.

For polyvinylchloride, polypropylene and PET, both directions oftransformation are possible; certain conditions exist for thepredominance of each one. The ratio of crosslinking to scissioning maydepend on several factors, including total irradiation dose, dose rate,the presence of oxygen, stabilizers, radical scavengers, and/orhindrances derived from structural crystalline forces.

Overall property effects of crosslinking can be conflicting andcontrary, especially in copolymers and blends. For example, after EBP,highly crystalline polymers like HDPE may not show significant change intensile strength, a property derived from the crystalline structure, butmay demonstrate a significant improvement in properties associated withthe behavior of the amorphous structure, such as impact and stress crackresistance.

Aromatic polyamides (Nylons) are considerably responsive to ionizingradiation. After exposure the tensile strength of aromatic polyamidesdoes not improve, but for a blend of aromatic polyamides with linearaliphatic polyamides, an increase in tensile strength is derivedtogether with a substantial decrease in elongation.

EBP may be used as an alternative to IR for more precise and rapidcuring of TPE coatings applied to preforms and containers.

It is believed that when used in conjunction with dip, spray, or flowcoating, EBP may have the potential to provide lower cost, improvedspeed and/or improved control of crosslinking when compared to IRcuring. EBP may also be beneficial in that the changes it brings aboutoccur in solid state as opposed to alternative chemical and thermalreactions carried out with melted polymer.

In other preferred embodiments, gas heaters, UV radiation, and flame maybe employed in addition to or in lieu of IR or EPB curing. Preferablythe drying/curing unit is placed at a sufficient distance or isolatedfrom the coating material tank and/or the flow coating sheet as to avoidunwanted curing of unused coating material.

5. Cooling

The preform is then cooled. The cooling process combines with the curingprocess to provide enhanced chemical, blush and scuff resistance. It isbelieved that this is due to the removal of solvents and volatiles aftera single coating and between sequential coatings.

In one embodiment the cooling process occurs at ambient temperature. Inanother embodiment, the cooling process is accelerated by the use offorced ambient or cool air.

There are several factors to consider during the cooling process. It ispreferable that the surface temperature of the preform is below theT_(g) of the lower of the T_(g) of the preform substrate or coating. Forexample, some coating materials have a lower T_(g) than the preformsubstrate material, in this example the preform should be cooled to atemperature below the T_(g) of the coating. Where the preform substratehas the lower T_(g) the preform should be cooled below the T_(g) of thepreform substrate.

Cooling time is also affected by where in the process the coolingoccurs. In a preferred embodiment multiple coatings are applied to eachpreform. When the cooling step is prior to a subsequent coating, coolingtimes may be reduced as elevated preform temperature is believed toenhance the coating process. Although cooling times vary, they aregenerally about 5 to 40 seconds for 24 gram preforms with about 0.05 toabout 0.75 grams of coating material.

6. Ejection from System

In one embodiment, once the preform has cooled it will be ejected fromthe system and prepared for packaging. In another embodiment the preformwill be ejected from the coating system and sent to a blow-moldingmachine for further processing. In yet another embodiment, the coatedpreform is handed off to another coating module where a further coat orcoats are applied. This further system may or may not be connected tofurther coating modules or a blow molding-machine.

7. Recycle

Advantageously, bottles made by, or resulting from, a preferred processdescribed above may be easily recycled. Using current recyclingprocesses, the coating can be easily removed from the recovered PET. Forexample, a polyhydroxyaminoether based coating applied by dip coatingand cured by IR heating can be removed in 30 seconds when exposed to an80° C. aqueous solution with a pH of 12. Additionally, aqueous solutionswith a pH equal to or lower than 4 can be used to remove the coating.Variations in acid salts made from the polyhydroxyaminoethers may changethe conditions needed for coating removal. For example, the acid saltresulting from the acetic solution of a polyhydroxyaminoether resin canbe removed with the use of an 80° C. aqueous solution at a neutral pH.Alternatively, the recycle methods set forth in U.S. Pat. No. 6,528,546,entitled Recycling of Articles Comprising Hydroxy-phenoxyether Polymers,may also be used. The methods disclosed in this application are hereinincorporated by reference.

8. Example

A lab scale flow coating system was used to coat 24 gram PET preforms. Asystem, as illustrated in FIGS. 14 through 16 was used, and comprised asingle flow coating unit with an IR curing/drying unit. The preformswere manually loaded onto the processing line. The collets used to holdthe 24 gram preforms were spaced 1.5″ on center from each other. It wasfound that this distance provided the proper spacing to avoid any wakeeffect while the preforms passed through the coating waterfall or sheet.The coating material was pumped into a tank using a non-shearing pump.The coating material then flowed out of the tank forming a waterfall orsheet that coated the preforms as they passed through the sheet. Thepreforms moved along the line at a rate of three inches per second inorder to ensure two full rotations while passing through the coatingsheet. Once through the sheet the line speed allowed the preforms todrip for approximately 10 seconds before passing over a sponge roller toremove an excess coating material from the bottom of the preform. Thepreforms then moved into the IR curing/drying unit. Five 1000 W GeneralElectric Q1500 T3/CL Quartzline Tungsten-Halogen lamps at 60% capacitywere used as the source. The lamps were positioned at 0.6 inches on thecenterline. The preforms remained in the IR curing/drying unit for about10 seconds. As the preforms moved out of the curing/drying unit theywere cooled for about 10 seconds with forced ambient air before beingremoved from the system.

The coating material used in this example was a PHAE dispersion, BLOX®XUR 588-29 (from The Dow Chemical Company), having 30% solids. Theaverage deposition (single layer on a 24 gram preform) was about 97 mg.

The various methods and techniques described above provide a number ofways to carry out the invention. Of course, it is to be understood thatnot necessarily all objectives or advantages described may be achievedin accordance with any particular embodiment described herein.

Furthermore, the skilled artisan will recognize the interchangeabilityof various features from different embodiments. Similarly, the variousfeatures and steps discussed above, as well as other known equivalentsfor each such feature or step, can be mixed and matched by one ofordinary skill in this art to perform methods in accordance withprinciples described herein.

Although the invention has been disclosed in the context of certainembodiments and examples, it will be understood by those skilled in theart that the invention extends beyond the specifically disclosedembodiments to other alternative embodiments and/or uses and obviousmodifications and equivalents thereof. Accordingly, the invention is notintended to be limited by the specific disclosures of preferredembodiments herein.

1. A container comprising: a substrate layer and a coating layer, thecoating layer having at least one layer comprising an acid salt of athermoplastic epoxy resin coating material disposed on at least aportion of said substrate layer.
 2. The container of claim 1, whereinthe acid salt is a reaction product of a thermoplastic epoxy resin andone or more of phosphoric acid, lactic acid, malic acid, citric acid,acetic acid, or glycolic acid.
 3. The container of claim 1, wherein thearticle exhibits substantially no blushing or whitening when exposed towater, wherein the exposure to water occurs for about 24 hours and withthe water at a temperature at about 0° C. to about 25° C.
 4. Thecontainer of claim 1, wherein the substrate layer comprises athermoplastic material selected from the group consisting of polyester,polypropylene, polyethylene, polycarbonate, polyamides and acrylics. 5.The container of claim 1, wherein the substrate layer comprisespolyethylene terephthalate.
 6. The container of claim 1, furthercomprising one or more layers of thermoplastic resin coating materialdisposed on said substrate layer.
 7. The container of claim 1, furthercomprising one or more layers of thermoplastic resin coating materialdisposed on said coating layer.
 8. The container of claim 1, furthercomprising an at least partially crosslinked outer layer.
 9. Thecontainer of claim 1, further comprising a top coat layer of a polyestermaterial.
 10. The container of claim 1, further comprising a top coatlayer of an acrylic.
 11. The container of claim 10, wherein the acrylicis partially or completed crosslinked.
 12. The container of claim 1,wherein the article is a preform or bottle having a body portion and aneck portion, and said coating layer is disposed substantially only onthe body portion of the preform or bottle.
 13. The container of claim 1,wherein the coating layer is applied by dip, spray, or flow coating. 14.A container comprising: a substrate having at least one layer comprisinga thermoplastic epoxy coating material obtained from curing/drying of asolution/dispersion of a thermoplastic epoxy polymer and an acid, the atleast one layer disposed on at least a portion of the substrate to formthe article.
 15. The container of claim 14, wherein the acid is one ormore of phosphoric acid, lactic acid, malic acid, citric acid, aceticacid, or glycolic acid.
 16. The container of claim 14, wherein thearticle exhibits substantially no blushing or whitening when exposed towater for about 24 hours and with the water at a temperature of about 0°C. to about 25° C.
 17. The container of claim 14, wherein the substratecomprises a thermoplastic material selected from the group consisting ofpolyester, polypropylene, polyethylene, polycarbonate, polyamides andacrylics.
 18. The container of claim 14, wherein the substrate comprisespolyethylene terephthalate.
 19. The container of claim 14, furthercomprising one or more layers of thermoplastic resin coating materialdisposed on said substrate.
 20. The container of claim 14, wherein thearticle is a preform or bottle having a body portion and a neck portion,and said coating layer is disposed substantially only on the bodyportion of the preform or bottle.
 21. The container of claim 14, whereinthe at least one layer is applied by dip, spray, or flow coating.
 22. Acontainer comprising: a first substrate layer comprising a thermoplasticmaterial selected from the group consisting of polyesters, polyolefins,polycarbonates, polyamides and acrylics; a second coating layercomprising a thermoplastic epoxy coating material, the thermoplasticepoxy coating material being a mixing product of a thermoplastic epoxypolymer and an organic acid or phosphoric acid; and wherein the secondcoating layer has a mass of about 0.05 g to about 0.55 g.
 23. Thecontainer of claim 22, wherein the second coating layer has a mass ofabout 0.06 g to about 0.2 g.
 24. The container of claim 22, wherein themixing product is a reaction product of a thermoplastic epoxy resin andone or more of phosphoric acid, lactic acid, malic acid, citric acid,acetic acid, or glycolic acid.
 25. The container of claim 22, whereinthe second coating layer is disposed on at least a portion of the firstsubstrate layer.
 26. The container of claim 22, wherein one or morelayers of thermoplastic resin coating material are disposed between thefirst substrate layer and the second coating layer.
 27. The container ofclaim 22, wherein the article comprises one or more layers having one ormore characteristics selected from the group consisting of gas-barrierprotection, UV protection, scuff resistance, blush resistance, andchemical resistance.
 28. The container of claim 22, wherein the articlecomprises amorphous or semi crystalline polyethylene terephthalate. 29.The container of claim 22, wherein the second coating layer is appliedby dip, spray, or flow coating.
 30. A container comprising an acid saltof a thermoplastic epoxy resin.
 31. The container of claim 30, whereinthe acid salt is a reaction product of the thermoplastic epoxy resin andone or more of phosphoric acid, lactic acid, malic acid, citric acid,acetic acid, or glycolic acid.
 32. The container of claim 30, whereinthe container comprises about 0.05 g to about 0.55 g of the acid salt.33. The container of claim 30, wherein the container comprises about0.06 g to about 0.2 g of the acid salt.